Arylamine containing polyhydroxy ether resins and system utilizing arylamine containing polyhydroxyl ether resins

ABSTRACT

An electrostatographic imaging member and an electrophotographic imaging process for using the imaging member are disclosed in which the imaging member comprises a substrate and at least one electrophotoconductive layer, the imaging member comprising a polymeric arylamine compound represented by the formula: ##STR1## wherein: R is selected from the group consisting of --H, --CH 3 , and --C 2  H 5  ; 
     m is between about 4 and about 1,000; 
     A is selected from the group consisting of an arylamine group represented by the formula: ##STR2## wherein: m is 0 or 1, 
     Z is selected from certain specified aromatic and fused ring groups that also contain an oxygen or sulfur atom, certain linear or cyclic hydrocarbon groups, and certain amine groups, 
     Ar is selected from certain specified aromatic groups, 
     Ar&#39; is selected from certain specified aromatic groups, and 
     B is selected from the group consisting of: 
     the arylamine group as defined for A and 
     
         --Ar--V).sub.n Ar-- 
    
     wherein: 
     Ar is as defined above, and 
     V is selected from an oxygen or sulfur atom, certain linear or cyclic hydrocarbon groups or a phenylene group, and 
     at least A or B contains the arylamine group. 
     The imaging member may comprise a substrate, charge generation layer and a charge transport layer.

BACKGROUND OF THE INVENTION

This invention relates in general to arylamine compounds and morespecifically, to polymeric tertiary arylamine compounds andelectrophotographic imaging members and processes utilizing suchpolymeric tertiary arylamine compounds.

In the art of electrophotography an electrophotographic plate comprisinga photoconductive insulating layer on a conductive layer is imaged byfirst uniformly electrostatically charging the surface of thephotoconductive insulating layer. The plate is then exposed to a patternof activating electromagnetic radiation such as light, which selectivelydissipates the charge in the illuminated areas of the photoconductiveinsulating layer while leaving behind an electrostatic latent image inthe non-illuminated areas. This electrostatic latent image may then bedeveloped to form a visible image by depositing finely dividedelectroscopic toner particles on the surface of the photoconductiveinsulating layer. The resulting visible toner image can be transferredto a suitable receiving member such as paper. This imaging process maybe repeated many times with reusable photoconductive insulating layers.

As more advanced, higher speed electrophotographic copiers, duplicatorsand printers were developed, degradation of image quality wasencountered during cycling. Moreover, complex, highly sophisticated,duplicating and printing systems operating at high speeds have placedstringent requirements including narrow operating limits onphotoreceptors. For example, the numerous layers found in many modernphotoconductive imaging members must be highly flexible, adhere well toto adjacent layers, and exhibit predictable electrical characteristicswithin narrow operating limits to provide excellent toner images overmany thousands of cycles. There is also a great current need for longservice life, flexible photoreceptors in compact imaging machines thatemploy small diameter support rollers for photoreceptor belt systemscompressed into a very confined space. Small diameter support rollersare also highly desirable for simple, reliable copy paper strippingsystems which utilize the beam strength of the copy paper toautomatically remove copy paper sheets from the surface of aphotoreceptor belt after toner image transfer. However, small diameterrollers, e.g less than about 0.75 inch (19 mm) diameter, raise thethreshold of mechanical performance criteria for photoreceptors to sucha high level that spontaneous photoreceptor belt material failurebecomes a frequent event for flexible belt photoreceptors.

One type of multilayered photoreceptor that has been employed as a beltin electrophotographic imaging systems comprises a substrate, aconductive layer, a charge blocking layer a charge generating layer, anda charge transport layer. The charge transport layer often comprises anactivating small molecule dispersed or dissolved in a polymeric filmforming binder. Generally, the polymeric film forming binder in thetransport layer is electrically inactive by itself and becomeselectrically active when it contains the activating molecule. Theexpression "electrically active" means that the material is capable ofsupporting the injection of either the hole or electron photogeneratedcharge carrier from the material in the charge generating layer and iscapable of allowing the transport of these charge carriers through theelectrically active layer in order to discharge a surface charge on theactive layer. The multilayered type of photoreceptor may also compriseadditional layers such as an anticurl backing layer, an adhesive layer,and an overcoating layer. Although excellent toner images may beobtained with multilayered belt photoreceptors that are developed withdry developer powder (toner), it has been found that these samephotoreceptors become unstable when employed wih liquid developmentsystems. These photoreceptors suffer from cracking, crazing,crystallization of active compounds, phase separation of activatingcompounds and extraction of activating compounds caused by contact withthe organic carrier fluid, isoparaffinic hydrocarbons, e.g. Isopar,commonly employed in liquid developer inks which, in turn, markedlydegrade the mechanical integrity and electrical properties of thephotoreceptor. More specifically, the organic carrier fluid of a liquiddeveloper tends to leach out activating small molecules, such as thearylamine containing compounds typically used in the charge transportlayers. Representative of this class of materials are:N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine;bis-(4-diethylamino-2-methylphenyl)-phenylmethane;2,5-bis-(4'-dimethylaminophenyl)-1,3,4,-oxadiazole;1-phenyl-3-(4'-diethylaminostyryl)-5-(4"-diethylaminophenyl)-pyrazoline;1,1-bis-(4-(di-N,N'-p-methylphenyl)-aminophenyl)-cyclohexane;4-diethylaminobenzaldehyde-1,1-diphenylhydrazone;1,1-diphenyl-2(p-N,N-diphenylaminophenyl)-ethylene;N-ethylcarbazole-3-carboxaldehyde-1-methyl-1-phenylhydroazone. Theleaching process results in crystallization of the activating smallmolecules, such as the aforementioned arylamine compounds, onto thephotoreceptor surface and subsequent migration of arylamines into theliquid developer ink. In addition, the ink vehicle, typically a C10-C14branched hydrocarbon, induces the formation of cracks and crazes in thephotoreceptor surface. These effects lead to copy defects and shortenedphotoreceptor life. The degradation of the photoreceptor manifestsitself as increased background and other printing defects prior tocomplete physical photoreceptor failure. The leaching out of theactivating small molecule also increases the susceptibility of thetransport layer to solvent/stress cracking when the belt is parked overa belt support roller during periods of non-use. Some carrier fluidsalso promote phase separation of the activating small molecules, such asarylamine compounds and their aforementioned derivatives, in thetransport layers, particularly when high concentrations of the arylaminecompounds are present in the transport layer binder. Phase separation ofactivating small molecules also adversely alters the electrical andmechanical properties of a photoreceptor. Although flexing is normallynot encountered with rigid, cylindrical, multilayered photoreceptorswhich utilize charge transport layers containing activating smallmolecules dispersed or dissolved in a polymeric film forming binder,electrical degradation are similarly encountered during development withliquid developers. Sufficient degradation of these photoreceptors byliquid developers can occur in less than eight hours of use therebyrendering the photoreceptor unsuitable for even low quality xerographicimaging purposes.

Photoreceptors have been developed which comprise charge transfercomplexes prepared with polymeric molecules. For example, chargetransport complexes formed with polyvinyl carbazole are disclosed inU.S. Pat. Nos. 4,047,948, 4,346,158 and 4,388,392. Photoreceptorsutilizing polyvinyl carbazole layers, as compared with currentphotoreceptor requirements, exhibit relatively poor xerographicperformance in both electrical and mechanical properties. Polymericarylamine molecules prepared from the condensation or di-secondary aminewith a di-iodo aryl compound are disclosed in European Pat. No. 34,425,published Aug. 26, 1981, issued May 16, 1984. Since these polymers areextremely brittle and form films which are very susceptible to physicaldamage, their use in a flexible belt configuration is precluded. Thus,in advanced imaging systems utilizing multilayered belt photoreceptorsexposed to liquid developement systems, cracking and crazing have beenencountered in critical charge transport layers during belt cycling.Cracks developing in charge transport layers during cycling can bemanifested as print-out defects adversely affecting copy quality.Furthermore, cracks in the photoreceptor pick up toner particles whichcannot be removed in the cleaning step and may be transferred to thebackground in subsequent prints. In addition, crack areas are subject todelamination when contacted with blade cleaning devices thus limitingthe options in electrophotographic product design.

Photoreceptors having charge transport layers containing small moleculearylamine compounds dispersed or dissolved in various resins such aspolycarbonates are known in the art. Similarly, photoreceptors utilizingpolymeric arylamine containing molecules such as polyvinyl carbazole,polymethacrylates possessing pendant arylamines are also known. Further,condensation polymers of a di-secondary amine with a di-iodo arylcompound are described in the prior art.

PRIOR ART STATEMENT

Canadian Pat. No. 11,171,431, corresponding to European Pat. No. 34,425to Xerox published Aug. 26, 1981, issued May 16, 1984--Condensationpolymers of a di-secondary amine with a di-iodo aryl compound aredescribed, for example, in working Examples IX and X.

Stolka et al, Photoconductivity and Hole Transport in Polymers ofAromatic Amine-Containing Methacrylates, Journal of Polymer Science:Polymer Chemistry Edition, Vol. 21,969 (1983)--Hole transport isdescribed in high molecular weight arylamine-substitutedpolymethacrylates. Synthesis of the monomers, their polymerization, andthe general properties of these polymers are also discussed.

U.S. Pat. No. 4,052,205 to Stolka et al, issued Oct. 4, 1977--Aphotoconductive imaging member is disclosed comprising various activepolymers, such as poly-N-vinyl carbazole, in a transport layer, e.g line45, column 5 to line 27, column 6. Derivatives of the active polymersmay be hydroxy substituted, e.g. column 5, lines 62-65.

U.S. Pat. No. 4,265,990 to Stolka et al, issued May 5, 1981--Transportlayers are disclosed comprising small molecule arylamines and apolycarbonate resin binder.

U.S. Pat. No. 4,415,641 to Goto et al, issued Nov. 15, 1983--Anelectrophotographic light-sensitive element is disclosed comprising acarbazole derivative (see column 3, lines 1-14). R₂ can represent ahydroxy group.

U.S. Pat. No. 4,588,666 to Stolka et al, issued May 13, 1986--A holetransporting molecule is disclosed comprising alkoxy derivatives oftetra phenyl biphenyl diamine (see column 3, lines 33-66). R₁ and R₂represent alkoxy groups which include methoxy. Resins such as polyvinylcarbazoles, polycarbonate resins, epoxy resins, polyvinyl butyrals,polyhydroxyether resins may be used as a binder for the holetransporting molecule.

U.S. Pat. No. 4,047,948 to A. M. Horgan, issued Sept. 13, 1977--Aphotoreceptor is disclosed comprising layers which may contain polyvinylcarbazole. The use of small molecule arylamine activating compounds intransport layers is also disclosed. The preferred small molecule resinbinder is a polycarbonate resin.

U.S. Pat. No. 4,346,158 to Pai et al, issued Aug. 24, 1982--Aphotoreceptor is disclosed comprising layers which may contain polyvinylcarbazole. The use of small molecule arylamine activating compounds intransport layers is also disclosed. The preferred small molecule resinbinder is a polycarbonate resin.

U.S. Pat. No. 4,388,392 to Kato et al, issued June 14, 1987--Aphotoreceptor is disclosed comprising layers which may contain polyvinylcarbazole. The use of an electron-donative polycyclic aromatichydrocarbon incorporated in an elctron-donative polymeric photoconductorin a charge transporting layer is also disclosed.

U.S. Pat. No. 4,273,846 to Pai et al, issued June 16, 1981--An imagingmember is disclosed comprising a polycarbonate resin material and anarylamine (see the general formula, column 2, lines 21-34). Poly-N-vinylcarbazole may be employed in the generator layer.

U.S. Pat. No. 3,844,781 to Tsuchiya et al, issued Oct. 29, 1974--Variousphotoconductive materials are disclosed containing substituents such ashydroxyl, amino and alkoxy groups.

U.S. Pat. No. 3,890,146 to Nagashima et al, issued June 17,1975--Various photoconductive materials are disclosed containingsubstituents such as hydroxyl, amino and alkoxy groups.

U.S. Pat. No. 4,588,667 to Jones, issued May 13, 1986--Variousovercoated electrophotographic imaging members are disclosed including amultilayered imaging member having a substrate, a titanium metal layer,a siloxane blocking layer, an adhesive layer, a charge generating binderlayer, and a charge transport layer. The transport layer may containfrom about 25 to about 75 percent by weight of arylamine transportmaterial in a resin binder such as polycarbonate resin.

Thus, there is a continuing need for multilayered photoreceptors havingimproved resistance to cracking, crazing, delamination, softening,swelling, crystallization of active compounds, phase separation ofactive compounds and leaching of active compounds. In addition to theink compatibility requirements the active compounds in charge transportlayers must also have high resistivity for charge retention, high holemobility for rapid discharge, and mechanical toughness for long life.

SUMMARY OF THE INVENTION

It is, therefore, an object of the present invention to provide animproved polymeric tertiary arylamine compound and a photoresponsivemember containing the polymeric compound which overcome the abovenoteddisadvantages.

It is yet another object of the present invention to provide an improvedelectrophotographic member which exhibits greater resistance to crackingand crazing induced by liquid ink carrier fluid.

It is yet another object of the present invention to provide an improvedelectrophotographic member which exhibits greater resistance to crackingand crazing when mechanically cycled in a belt-type configuration arounda narrow diameter roller.

It is a further object of the present invention to provide aphotoconductive imaging member which exhibits improved resistance tocomponent leaching during liquid development.

It is still another object of the present invention to provide aphotoconductive imaging member which exhibits improved resistance tocomponent crystallization.

It is a further object of the present invention to provide anelectrophotographic imaging member which retains stable electricalproperties during cycling.

It is yet another object of the present invention to provide an improvedelectrophotographic member which resists abrasion when exposed to bladecleaning devices.

It is a further object of the present invention to provide an improvedphotoconductive imaging member which exhibits resistance to softeningand swelling when exposed to liquid ink carrier fluid.

The foregoing objects and others are accomplished in accordance withthis invention by providing a polymeric arylamine compound representedby the formula: ##STR3## wherein: R is selected from the groupconsisting of --H, --CH₃, and --C₂ H₅ ;

m is between about 4 and about 1,000; and

A is selected from the group consisting of an arylamine grouprepresented by the formula: ##STR4## wherein: m is 0 or 1,

Z is selected from the group consisting of: ##STR5## wherein: n is 0 or1,

Ar is selected from the group consisting of: ##STR6## wherein: R isselected from the group consisting of --CH₃, --C₂ H₅, --C₃ H₇, and --C₄H₉,

Ar' is selected from the group consisting of: ##STR7## X is selectedfrom the group consisting of: ##STR8## and B is selected from the groupconsisting of: the arylamine group as defined for A, and

    --Ar--V).sub.n Ar--

wherein Ar is as defined above, and V is selected from the groupconsisting of: ##STR9## and at least A or B contains the arylaminegroup.

The polymeric arylamine compound of this invention is utilized in anelectrophotographic imaging member comprising a substrate having anelectrically conductive surface, a charge blocking layer, a chargegeneration layer, and a hole transport layer, at least the chargegeneration layer or charge transport layer containing the abovedescribed polymeric arylamine compound of this invention.

The electrophotographic imaging member of this invention may be employedin any suitable electrophotographic imaging process.

Generally, the polymeric arylamine compounds of this invention may beprepared by reacting a hydroxy compound selected from the groupconsisting of a hydroxy arylamine represented by the formula: ##STR10##wherein: m, Ar, Ar' and Z are as defined above, and a hydroxydiphenylene group represented by the formula:

    HO--Ar--V).sub.n Ar--OH

wherein:

Ar and V are as defined above with a reactant selected from the groupconsisting of:

a diglycidyl arylamine compound represented by the formula: ##STR11##wherein: m, Z, Ar, and Ar' are as defined above, and a diglycidyldiphenylene compound represented by the formula: ##STR12## wherein: Ar,V and n are as defined above, and wherein at least one of the reactantscontains the arylamine group represented by the formula: ##STR13##wherein: m, Z, Ar and Ar' are as defined above.

A catalyst may be used in the reaction. Typical catalysts include asammonium carbonate, ammonium acetate, ammonium bicarbonate, potassiumcarbonate, triethanol amine, triphenyl phosphine, benzyl trimethylammonium hydroxide, and tetramethyl ammonium hydroxide.

A triphenyl phosphine is preferred because it greatly shortens thereaction time.

If desired, the hydroxyl end groups on the resulting polymeric arylaminemay be converted to alkoxy end groups by treatment with a strong basesuch as KOH and an alkylating agent such as CH₃ l, C₂ H₅ l, and thelike. Replacement of the OH end groups wih alkoxy groups is criticalwhen the OH groups are located in the para position on the end phenylenegroup of the arylamine moiety of the polymer because such polymers causeunacceptably high levels of charge trapping in electrophotographicimaging members utilizing the polymer.

The foregoing reaction may be represented by the following generalequation: ##STR14##

Compounds represented by the above hydroxy arylamine formula may beprepared by hydrolyzing an alkoxy arylamine. A typical process forpreparing alkoxy arylamines is disclosed in Example 1 of U.S. Pat. No.4,588,666 to Stolka et al, the entire disclosure of this patent beingincorporated herein by reference. In accordance with the procedure ofExample 1 in U.S. Pat. No. 4,588,666,N,N'-di(3-methoxyphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'diamine wassynthesized from m-iodoanisole to achieve a yield of 90 percent, m.p.120°-125° C.N,N'diphenyl-N,N'-bis(3-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine wasprepared, for example, from theN,N'-di(3-methoxyphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'diamine byplacing into a two liter three-necked round bottom flask, equipped witha mechanical stirrer and an argon gas inlet, 137.5 gmsN,N'-diphenyl-N,N'-bis(3-methoxyphenyl)-[1,1'-biphenyl]-4,4'diamine(0.25 moles), 223.5 gms anhydrons sodium iodide (1.5 moles) and 500millileters warm sulfolane (distilled). The contents of the flask wereheated to 120° C. then cooled to 60° C. Five millileters of D.I. waterwas added dropwise, followed by 190.5 millileters oftrimethyl(-chlorosilane (1.5 moles)). The contents were allowed to heatat 60°-75° C. for six hours. HPLC analysis was utilized to determinewhen the reaction was complete. The contents of the flask were pouredinto a 3 liter Erlenmeyer flask containing 1.5 liter of deionized water.The water layer was decanted and the dark oily residue taken up into 500milliliters methanol. The methanol solution was extracted with two 400milliliter portions of hexane to remove the hexamethyldisiloxaneby-products. The methanol solution was roto-evaported to remove thesolvents. The residue was taken up into 500 milliliters of acetone andthen precipitated into 1.5 liters deionized water. The off-white solidwas filtered and then washed with deionized water and dried in vacuo.The crudeN,N'diphenyl-N,N'-bis(3-hydroxyphenyl)[1,1'-biphenyl]-4,4'-diamine wasplaced into a two liter round-bottom flask containing a magnetic stirrerand one liter toluene. Fifty gms. Florisil® (Florisil is a registeredtrademark of Floridin Co.) was added to the flask and allowed to stirfor two hours. The dark Florisil® was filtered off, leaving a pale yelowtoluene solution. The toluene was roto-evaporated to yield a pale yellowviscous oil. The oily product was dissolved in 400 milliliters acetonethen diluted with 400 milliliters heptane and allowed to crystallize.The colorless crystals were filtered. Additional product was obtained byroto-evaporating the acetone from the filtrate. Yield was 85 percent,m.p. 113°-17° C. Typical compounds represented by the above formula forhydroxy arylamine compounds include: ##STR15##

Compounds represented by the above formula includeN,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine;N,N-di(4-hydroxyphenyl)-m-toluidine;bis-(N-(3-hydroxyphenyl)-N-phenyl-4-aminophenyl)-methane;bis[(N-(4-hydroxyphenyl)-N-phenyl)-4-aminophenyl]-isopropylidene;N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)[1,1':4',1"-terphenyl]-4,4"-diamine;9-ethyl-3.6-bis[N-phenyl-N-3(3-hydroxyphenyl)-amino]-carbazole;1,4-bis[N-phenyl-N-(3-hydroxyphenyl)]phenylenediamine; and the like.

Typical compounds represented by the above formula for hydroxydiphenylene compounds include: ##STR16##

Compounds represented by the above formula for diglycidyl are di(4-hydroyphenyl) ether; di (3-hydroyphenyl) ether; di (4-hydroyphenyl)methane; di (3-hydroyphenyl) methane; di (3-hydroyphenyl)isopropylidene; di (4-hydroyphenyl) isopropylidene; di (4-hydroyphenyl)thioether; and 4,4"-dihydroxy-1,1':3',1"-terphenyl; and the like.

Compounds represented by the above formula for diglycidyl arylaminecompounds can be prepared by the above formula with epibromohydrin orepichlorohydrin (Aldrich Chemical). A typical reaction is run usingN-methyl pyrolidinone, 200 milliliters (mls) through which Argon isbubbled for about 10 minutes. Eleven (11) grams of powdered KOH was thenadded with stirring. This mixture was stirred for about 20 minutes.N,N'-diphenyl-N,N'-4-hydroxyphenyl-[1,1'-biphenyl]-4,4'diamine (0.078mole), 42.8 grams, was then added particlewise with stirring. Afterdissolution, the reaction mixture is cooled to about 10° C.Epibromohydrin is added dropwise with stirring. After one half ofaddition is complete, the ice bath was removed, and the addition wascompleted. The reaction was allowed to stir for 2 hours after theaddition was complete. The reaction is quenched in water. The productisolated could be recrystallized with difficulty from ethyl alcohol. 30grams were isolated, about 50 percent yield.

Typical compounds represented by the above formula for diglycidylarylamine compounds include: ##STR17##

Compounds represented by the above formula includeN,N'-diphenyl-N,N'-bis(3-(2,3-epoxypropxy)phenyl)-[1,1'-biphenyl]-4,4'-diamine;N,N-di(4-(2,3-epoxypropoxy)-phenyl)-aniline;1,1-bis(4-(N-3-(2,3-epoxypropoxy)phenyl)-4-(N-phenyl)-aminophenyl)-cyclohexane;bis[N-(3-(2,3-epoxypropoxy)phenyl)-N-phenyl-4-aminophenyl]-methane;bis[N-(4-(2,3-epoxypropoxy)phenyl)-N-phenyl-4-aminophenyl]-isopropylidene;N,N'-diphenyl-N,N'-bis(3-(2,3-epoxypropoxy)phenyl)-[1,1':4',1"-terphenyl]-4,4"-diamine;9-ethyl-3,6-bis[N-phenyl-N-(3-(2,3-epoxypropxy)phenyl)-amino]-carbazole;1,4-bis[N-phenyl-N-(2,3-epoxypropoxy)phenyl)]-phenylenediamine; and thelike.

Typical compounds represented by the above formula fordiglycidyldiphenylene compounds include: ##STR18##

Compounds represented by the above formula include di(4-(2,3-epoxypropxy)phenyl)-ether; di(3-(2,3-epoxypropoxy)phenyl)-ether; di(4-(2,3-epoxypropoxy)phenyl)-methane; di(3-(2,3-epoxypropoxy)phenyl)-isopropylidene; di(4-(2,3-epoxypropoxy)phenyl)-isopropylidene; di(4-(2,3-epoxypropoxy)phenyl)-thioether; 4,4"-di(2,3-epoxypropoxy)-1,1':3',1"-terphenyl; and the like.

The following is an illustrative reaction between a specific diglycidyldiphenylene compound and a specific dihydroxy arylamine compoundfollowed by replacement of the hydroxyl group on the resulting polymerwith a methoxy group: ##STR19##

The value of m was between about 18 and about 19.

Preparation of polyhydroxy ether resin, phenoxy resin based onN,N'-di(4-hydroxyphenyl)-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine, andbis(4-(2,3-epoxypropoxy)phenyl)-isopropylidene:

To the reaction vessel are placed 5.2 grams (0.01 mole) of the dihydroxyarylamine compound and 3.4 grams (0.01 mole) of the diglycidyldiphenylene compound, 5 cc of p-dioxane and 0.52 gram (10⁻² mole/eq.weight of epoxide) of triphenyl phosphine (C₆ H₅)₃ P. The reactionmixture was heated to, and maintained at 102° C.±1 for 9 days. The veryviscous mass, which solidifies to a glass upon cooling to roomtemperature, was dissolved in a minimum of THF, and isolated by slowlyadding to 500 cc of MeOH in a Waring blender. Yield 85.6 percent.

The allylation of the phenoxy polymer is carried out in N-methylpyrolidinone (Alrdich Chemical Company), 10 milliliters (mls) in which 4grams of the polymer was dissolved. To this solution is added 1 gram ofpowdered KOH. To the now yellow solution was added CH₃ l, 2 mls, dilutedwith 5 mls of N-methyl pyrolidinone. This was allowed to stir for about2 hours. The reaction was quenched in 50 cc of MeOH. The white ppt wascollected by filtration. The infrared spectrum indicated all OH areblacked.

The polymeric reaction product prior to methylation contained arigid-rod like transporting arylamine moiety from the dihydroxyarylamine reactant in alternation with a flexibilizing unit derived fromthe diglycidyl-bis-phenol coreactant which imparted good mechanicalproperties to the polymer. From the infrared spectrum of polymer priorto methylation, it was determined that many of the end groups possessedthe hydroxyl group of the dihydroxyl arylamine starting material. Whenthis polymer was cast as a 20 micrometer thick film on an amorphousselenium photogenerator layer and tested for electrical properties, thedevice exhibited such high levels of trapping that it could not be usedin xerographic applications despite the fact that the polymer possessedgood film forming and mechanical properties. However, when the polymericreaction product prior to methylation was converted to the fullymethylated polymer, B, (including both the phenolic end groups as wellas the hydroxyl units in the backbone) by treatment with base (KOH) andthe methylating agent, CH₃ l, electrical evaluation of the methylatedpolymer under the same test conditions as the polymeric reaction productprior to methylation, revealed that the methylated polymer functionedwell in a hole transporting capacity, i.e. it possessed high mobilityand low residual. It appears that for achievement of good holetransporting capacity, methylation is required only when the hydroxylgroup is located at the para position on the phenylene group of thearylamine moiety. Methylation is unnecessary when the hydroxyl group islocated at the meta or ortho positions on the phenylene group of thearylamine moiety.

The following is an illustrative reaction between a specific diglycidylarylamine compound and a specific dihydroxy arylamine compound:##STR20##

The value of m was between about 4 and about 5.

Preparation of polyhydroxyether resin phenoxy resin based onN,N'-diphenyl-N,N'-bis(4-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine,and N,N'-diphenyl-N,N-bis(4-(2,3-epoxypropoxy)phenyl)-[1,1'-biphenyl]-4,4'-diamine:

The two reactants, 3.16 grams of the diepoxy arylamine compound, and 2.6grams of the dihydroxy arylamine compound are placed in a reactionvessel with 2 cc of dioxane and 0.026 gram of triphenyl phosphene. Thereaction was heated to and maintained at 105° C. for 3 days. Dioxane wasadded during this reaction period to maintain a viscosity suitable forstirring. The almost gel-like product was dissolved in N-Methylpyrolidinone and dioxane. The polymer was precipitation was accomplishedwith MeOH. Yield obtained was 78 percent.

Unlike the polymer produced in the immediately preceding reaction, thenumber of phenolic end groups attached to the transporting moiety hasbeen substantially reduced and the content of transporting moiety hasbeen increased from 57.8 percent to 85.1 percent by weight. Althoughthis polymer contains a hydroxyl group located at the para position onthe phenylene group of the arylamine moiety, this polymer transportsholes without a subsequent methyl blocking step. In addition, thispolymer produced by a reaction between diglycidyl arylamine compound anda dihydroxy arylamine compound is capable of forming interchain hydrogenbonds. This phenomena adds greatly to its mechanical strenght and inaddition, increases the oleophobicity relative to polymers in whichhydrogen bonding is not possible. All synthesis steps leading to thepolymer as well as the polymerization process itself are high yield.

Any suitable solvent may be employed to dissolve the reactants. Typicalsolvents include dioxane, tetrahydrofuran, and the like. Satisfactoryyields are achieved with reaction temperatures between about 80° C. andabout 110° C. The reaction temperature selected depends to some extenton the specific reactants utilized and specific catalyst used. Thereaction temperature may be maintained by any suitable technique such asheating mantles, radiant heat lamps, oil baths, and the like.

The reaction time depends upon the reaction temperatures and reactantsused. Thus, less reaction time is required when higher reactiontemperatures are employed. Generally, increasing the reaction timeincreases the degree of polymerization. Satisfactory results have beenachieved with reaction times between about 3 days to about 9 days atabout 102° C. and about 105° C. For practical purposes, sufficientdegree of polymerizatio is achieved by the time the reaction product isunable to be stirred at the reaction temperature.

The reaction may be conducted under any suitable pressure includingatmospheric pressure.

One may readily determine whether sufficient reaction product has beenformed by monitoring viscosity. Typical polymeric arylamine compounds ofthis invention include, for example ##STR21##

Preferred polymeric arylamines of this invention have a molecular weightfrom about 4,000 to about 40,000. The polyhydroxyether resins resultsfrom the reaction ofN,N'-diphenyl-N,N'-bis[3-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine,and bis(4-(2,3-epoxypropoxy)phenyl)-isopropylidene is a preferred resinpossessing no para hydroxy substituted arylamine end groups. Thisresults in the best hole transport with no subsequent reaction required.It also retains the hydroxyl functionality in the backbone resulting ingood physical properties. The material most preferred is of thefollowing formula ##STR22##

A photoconductive imaging member of this invention may be prepared byproviding a substrate having an electrically conductive surface,applying a charge blocking layer on the electrically conductive surface,applying a charge generation layer on the blocking layer and applying acharge transport layer on the charge generation layer. If desired, thecharge transport layer may be applied to the electrically conductivesurface and the charge generation layer may thereafter be applied to thecharge transport layer. The polymeric arylamine of this invention ispresent in at least the charge generation layer or the charge transportlayer. When the photoconductive imaging member of this invention isemployed in liquid development systems, the polymeric arylamine of thisinvention is preferably present in at least the outermost layer of theimaging member.

The substrate may be opaque or substantially transparent and maycomprise numerous suitable materials having the required mechanicalproperties. Accordingly, the substrate may comprise a layer of anelectrically non-conductive or conductive material such as an inorganicor an organic composition. As electrically non-conducting materialsthere may be employed various resins known for this purpose includingpolyesters, polycarbonates, polyamides, polyurethanes, and the like. Theelectrically insulating or conductive substrate may be rigid or flexibleand may have any number of different configurations such as, forexample, a cylinder, sheet, a scroll, an endless flexible belt, and thelike. Preferably, the substrate is in the form of an endless flexiblebelt and comprises a commercially available biaxially oriented polyesterknown as Mylar, available from E. I. du Pont de Nemours & Co. or Melinexavailable from ICI.

The thickness of the substrate layer depends on numerous factors,including economical considerations, and thus a layer for a flexiblebelt may be of substantial thickness, for example, over 200 micrometers,or of minimum thickness less than 50 micrometers, provided there are noadverse affects on the final photoconductive device. In one flexiblebelt embodiment, the thickness of this layer ranges from about 65micrometers to about 150 micrometers, and preferably from about 75micrometers to about 125 micrometers for optimum flexibility and minimumstretch when cycled around small diameter rollers, e.g. 12 millimeterdiameter rollers. The surface of the substrate layer is preferablycleaned prior to coating to promote greater adhesion of the depositedcoating. Cleaning may be effected by exposing the surface of thesubstrate layer to plasma discharge, ion bombardment and the like.

The conductive layer may vary in thickness over substantially wideranges depending on the optical transparency and flexibility desired forthe electrophotoconductive member. Accordingly, when a flexiblephotoresponsive imaging device is desired, the thickness of theconductive layer may be between about 20 angstrom units to about 750angstrom units, and more preferably from about 50 Angstrom units toabout 200 angstrom units for an optimum combination of electricalconductivity, flexibility and light transmission. The conductive layermay be an electrically conductive metal layer formed, for example, onthe substrate by any suitable coating technique, such as a vacuumdepositing technique. Typical metals include aluminum, zirconium,niobium, tantalum, vanadium and hafnium, titanium, nickel, stainlesssteel, chromium, tungsten, molybdenum, and the like. If desired, analloy of suitable metals may be deposited. Typical metal alloys maycontain two or more metals such as zirconium, niobium, tantalum,vanadium and halfnium, titanium, nickel, stainless steel, chromium,tungsten, molybdenum, and the like, and mixutes thereof. Regardless ofthe technique employed to form the metal layer, a thin layer of metaloxide forms on the outer surface of most metals upon exposure to air.Thus, when the other layers overlying the metal layer are characterizedas "contiguous" layers, it is intended that these overlying contiguouslayers may, in fact, contact a thin metal oxide layer that has formed onthe outer surface of the oxidizable metal layer. Generally, for rearerase exposure, a conductive layer light transparency of at least about15 percent is desirable. The conductive layer need not be limited tometals. Other examples of conductive layers may be combinations ofmaterials such as conductive indium tin oxide as a transparent layer forlight having a wavelength between about 4000 Angstroms and about 7000Angstroms or a conductive carbon black dispersed in a plastic binder asan opaque conductive layer.

After deposition of the metal layer, a hole blocking layer may beapplied thereto. Generally, electron blocking layers for positivelycharged photoreceptors allow holes from the imaging surface of thephotoreceptor to migrate toward the conductive layer. Any suitableblocking layer capable of forming an electronic barrier to holes betweenthe adjacent photoconductive layer and the underlying conductive layermay be utilized. The blocking layer may be organic or inorganic and maybe deposited by any suitable technique. For example, if the blockinglayer is soluble in a solvent, it may be applied as a solution and thesolvent can subsequently be removed by any conventional method such asby drying. Typical blocking layers include polyvinylbutyral,oranosilanes, epoxy resins, polyesters, polyamides, polyurethanes,pyroxyline vinylidene chloride resin, silicone resins, fluorocarbonresins and the like containing an organo metallic salt. Other blockinglayer materials include nitrogen containing siloxanes or nitrogencontaining titanium compounds such as trimethoxysilyl propylene diamine,hydrolyzed trimethoxysilyl propyl ethylene diamine, N-beta-(aminoethyl)gamma-amino-propyl trimethoxy silane, isopropyl 4-aminobenzene sulfonyl,di(dodecylbenzene sulfonyl) titanate, isopropyldi(4-aminobenzoyl)isostearoyl titanate, isopropyltri(N-ethylamino-ethylamino)titanate, isopropyl trianthranil titanate,isopropyl tri(N,N-dimethyl-ethylamino)titanate, titanium-4-amino benzenesulfonat oxyacetate, titanium 4-aminobenzoate isostearate oxyacetate,[H₂ N(CH₂)₄ ]CH₃ Si(OCH₃)₂, (gamma-aminobutyl) methyl diethoxysilane,and [H₂ N(CH₂)₃ ]CH₃ Si(OCH₃)₂ (gamma-aminopropyl) methyldiethoxysilane, as disclosed in U.S. Pat. Nos. 4,291,110, 4,338,387,4,286,033 and 4,291,110. The disclosures of U.S. Pat. Nos. 4,338,387,4,286,033 and 4,291,110 are incorporated herein in their entirety. Apreferred blocking layer comprises a reaction product between ahydrolyzed silane and the oxidized surface of a metal ground planelayer. The oxidized surface inherently forms the outer surface of mostmetal ground plane layers when exposed to air after deposition. Thiscombination enhances electrical stability at low RH. The hydrolyzedsilane has the general formula: ##STR23## or mixtures thereof, whereinR₁ is an alkylidene group containing 1 to 20 carbon atoms, R₂, R₃ and R₇are independently selected from the group consisting of H, a lower alkylgroup containing 1 to 3 carbon atoms and a phenyl group, X is an anionof an acid or acidic salt, n is 1, 2, 3 or 4, and y is 1, 2, 3 or 4.

The imaging member is preferably prepared by depositing on the metaloxide layer of a metal conductive anode layer, a coating of an aqueoussolution of the hydrolyzed aminosilane at a pH between about 4 and about10, drying the reaction product layer to form a siloxane film andapplying an adhesive layer of this invention, and thereafter applyingelectrically operative layers, such as a photogenerator layer and a holetransport layer, to the siloxane film.

The blocking layer should be continuous and have a thickness of lessthan about 0.5 micrometer because greater thickness may lead toundesirably high residual voltage. A blocking layer of between about0.005 micrometer and about 0.3 micrometer (50 Angstroms-3000 Angstroms)is preferred because charge neutralization after the exposure step isfacilitated and optimum electrical performance is achieved. A thicknessof between about 0.3 micrometer and about 0.06 micrometer is preferredfor metal oxide layers for optimum electrical behavior. Optimum resultsare achieved with a siloxane blocking layer. The blocking layer may beapplied by any suitable conventional technique such as spraying, dipcoating, draw bar coating, gravure coating, silk screening, air knifecoating, reverse roll coating, vacuum deposition, chemical treatment andthe like. For convenience in obtaining thin layers, the blocking layersare preferably applied in the form of a dilute solution, with thesolvent being removed after deposition of the coating by conventionaltechniques such as by vacuum, heating and the like. Generally, a weightratio of blocking layer material and solvent of between about 0.05:100and about 0.5:100 is satisfactory for spray coating. This siloxanecoating is described in U.S. Pat. No. 4,464,450 to L. A. Teuscher, thedisclosure of this patent being incorporated herein in its entirety.

If desired, any suitable adhesive layer may be applied to the holeblocking layer. Typical adhesive layers include a polyester resin suchas Vitel PE-100, Vitel PE-200, Vitel PE-200D, and Vitel PE-222, allavailable from Goodyear Tire and Rubber Co., polyvinyl butyral, duPont49,000 polyester, and the like. When the adhesive layer is employed, itshould be continuous and preferably, has a dry thickness between about200 micrometers and about 900 micrometers and more preferably betweenabout 400 micrometers and about 700 micrometers. Any suitable solvent orsolvent mixtures may be employed to form a coating solution of theadhesive layer material. Typical solvents include tetrahydrofuran,toluene, methylene chloride, cyclohexanone, and the like, and mixturesthereof. Generally, to achieve a continuous adhesive layer thickness ofabout 900 angstroms or less by gravure coating techniques, the solidsconcentration are between about 2 percent and about 5 percent by weightbased on the total weight of the coating mixture of resin and solvent.However, any other suitable and conventional technique may be utilizedto mix and thereafter apply the adhesive layer coating mixture to thecharge blocking layer. Typical application techniques include spraying,dip coating, roll coating, wire wound rod coating, and the like. Dryingof the deposited coating may be effected by any suitable conventionaltechnique such as oven drying, infra red radiation drying, air dryingand the like.

Any suitable photogenerating layer may be applied to the blocking layeror intermediate layer if one is employed, which can then be overcoatedwith a contiguous hole transport layer as described. Examples ofphotogenerating layers include inorganic photoconductive particles suchas amorphous selenium, trigonal selenium, and selenium alloys selectedfrom the group consisting of selenium-tellurium,selenium-tellurium-arsenic, selenium arsenide and mixtures thereof, andorganic photoconductive particles including various phthalocyaninepigment such as the X-form of metal free phthalocyanine described inU.S. Pat. No. 3,357,989, metal phthalocyanines such as vanadylphthalocyanine and copper phthalocyanine, quinacridones available fromDuPont under the tradename Monastral Red, Monastral violet and MonastralRed Y, Vat orange 1 and Vat orange 3 trade names for dibromo antanthrone pigments, benzimidazole perylene, substituted2,4-diamino-triazines disclosed in U.S. Pat. No. 3,442,781, polynucleararomatic quinones available from Allied Chemical Corporation under thetradename Indofast Double Scarlet, Indofast Violet Lake B, IndofastBrilliant Scarlet and Indofast Orange, and the like dispersed in a filmforming polymeric binder. Selenium, selenium alloy, benzimidazoleperylene, and the like and mixtures thereof may be formed as acontinuous, homogeneous photogenerating layer. Benzimidazole perylenecompositions are well known and described, for example in U.S. Pat. No.4,587,189, the entire disclosure thereof being incorporated herein byreference. Multiphotogenerating layer compositions may be utilized wherea photoconductive layer enhances or reduces the properties of thephotogenerating layer. Examples of this type of configuration aredescribed in U.S. Pat. No. 4,415,639, the entire disclosure of thispatent being incorporated herein by reference. Other suitablephotogenerating materials known in the art may also be utilized, ifdesired. Charge generating binder layer comprising particles of layerscomprising a photoconductive material such as vanadyl phthalocyanine,metal free phthalocyanine, benzimidazole perylene, amorphous selenium,trigonal selenium, selenium alloys such as selenium-tellurium,selenium-tellurium-arsenic, selenium arsenide, and the like and mixturesthereof are especially preferred because of their sensitivity to whitelight. Vanadyl phthalocyanine, metal free phthalocyanine and telluriumalloys are also preferred because these materials provide the additionalbenefit of being sensitive to infra-red light.

Numerous inactive resin materials may be employed in the photogeneratingbinder layer including those described, for example, in U.S. Pat. No.3,121,006, the entire disclosure of which is incorporated herein byreference. Typical organic resinous binders include thermoplastic andthermosetting resins such as polycarbonates, polyesters, polyamides,polyurethanes, polystyrenes, polyarylethers, polyarylsulfones,polybutadienes, polysulfones, polyethersulfones, polyethylenes,polypropylenes, polyimides, polymethylpentenes, polyphenylene sulfides,polyvinyl acetate, polysiloxanes, polyacrylates, polyvinyl acetals,polyamides, polyimides, amino resins, phenylene oxide resins,terephthalic acid resins, epoxy resins, phenolic resins, polystyrene andacrylonitrile copolymers, polyvinylchloride, vinylchloride and vinylacetate copolymers, acrylate copolymers, alkyd resins, cellulosic filmformers, poly(amideimide), styrene-butadiene copolymers,vinylidenechloride-vinylchloride copolymers,vinylacetate-vinylidenechloride copolymers, styrene-alkyd resins, andthe like. These polymers may be block, random or alternating copolymers.

Active carrier transporting resin may also be employed as the binder inthe photogenerating layer. These resins are particularly useful wherethe concentration of carrier generating pigment particles is low and thethickness of the carrier generation layer is substantially thicker thanabout 0.7 micrometer. The active resin commonly used as a binder ispolyvinylcarbazole whose function is to transport carriers which wouldotherwise be trapped in the layer.

The electrically active polymeric amines of this invention can beemployed in the generation layer replacing the polyvinylcarbazole binderor any other active or inactive binder.

Part or all of the active resin materials to be employed in thegenerator layer may be replaced by the electrically active polymericarylamines of this invention.

The photogenerating composition or pigment is present in the resinousbinder composition in various amounts, generally, however, from about 5percent by volume to about 90 percent by volume of the photogeneratingpigment is dispersed in about 10 percent by volume to about 95 percentby volume of the resinous binder, and preferably from about 20 percentby volume to about 30 percent by volume of the photogenerating pigmentis dispersed in about 70 percent by volume to about 80 percent by volumeof the resinous binder composition. In one embodiment about 8 percent byvolume of the photogenerating pigment is dispersed in about 92 percentby volume of the resinous binder composition.

For embodiments in which the photogenerating layers do not contain aresinous binder, the photogenerating layer may comprise any suitable,well known homogeneous photogenerating material. Typical homogeneousphotogenerating materials include inorganic photoconductive compoundssuch as amorphous selenium, selenium alloys selected such asselenium-tellurium, selenium-tellurium-arsenic, and selenium arsenideand organic materials such as chlorindium phthalocyanine, chloraluminumphthalocyanine, vanadyl phthalocyanine, and the like.

The photogenerating layer containing photoconductive compositions and/orpigments and the resinous binder material generally ranges in thicknessof from about 0.1 micrometer to about 5.0 micrometers, and preferablyhas a thickness of from about 0.3 micrometer to about 3 micrometers. Thephotogenerating layer thickness is related to binder content. Higherbinder content compositions generally require thicker layers forphotogeneration. Thickness outside these ranges can be selectedproviding the objectives of the present invention are achieved.

The active charge transport layer comprises a polymeric aryl amine ofthis invention capable of supporting the injection of photogeneratedholes from the charge generation layer and allowing the transport ofthese holes through the transport layer to selectively discharge thesurface charge. When the photogenerating layer is sandwiched between theconductive layer and the active charge transport layer, the transportlayer not only serves to transport holes, but also protects thephotoconductive layer from abrasion or chemical attack and thereforeextends the operating life of the electrophotographic imaging member.The charge transport layer should exhibit negligible, if any, dischargewhen exposed to a wavelength of light useful in xerography, e.g. 4000angstroms to 9000 angstroms. Therefore, the charge transport layer issubstantially transparent to radiation in a region in which thephotoconductor is to be used. Thus, the active charge transport layer isa substantially non-photoconductive material which supports theinjection of photogenerated holes from the generation layer. The activetransport layer is normally transparent when exposure is effectedthrough the active layer to ensure that most of the incident radiationis utilized by the underlying charge carrier generator layer forefficient photogeneration. When used with a transparent substrate,imagewise exposure may be accomplished through the substrate with alllight passing through the substrate. In this case, the active transportmaterial need not be transmitting in the wavelength region of use. Thecharge transport layer in conjunction with the generation layer in theinstant invention is a material which is an insulator to the extent thatan electrostatic charge placed on the transport layer is not conductedin the absence of illumination.

Part or all of the transport material comprising a hole transportingsmall molecule in an inactive binder to be employed in the transportlayer may be replaced by the active materials of this inventiondescribed above comprising a polymeric arylamine film forming material.Any substituents in the polymeric arylamine compound should be free fromelectron withdrawing groups such as NO₂ groups, CN groups, and the like.The hole transporting small molecule-inactive resin binder compositionmay be entirely replaced with 100 percent of a polymeric arylaminecompound of this invention.

Any suitable solvent may be employed to apply the transport layermaterial to the underlying layer. Typical solvents include methylenechloride, toluene, tetrahydrofuran, and the like. Methylene chloridesolvent is a particularly desirable component of the charge transportlayer coating mixture for adequate dissolving of all the components andfor its low boiling point.

An especially preferred transport layer employed in one of the twoelectrically operative layers in the multilayer photoconductor of thisinvention comprises from about 50 percent to about 100 percent by weightof poly[3,3'-bis(hydroxyethyl)tetraphenylbenzidene]carbonate and fromabout 0 percent to about 50 percent by weight ofbisphenol-A-polycarbonate.

Any suitable and conventional technique may be utilized to mix andthereafter apply the charge transport layer coating mixture to theunderlying surface, e.g. charge generating layer. Typical applicationtechniques include spraying, dip coating, roll coating, wire wound rodcoating, and the like. Drying of the deposited coating may be effectedby any suitable conventional technique such as oven drying, infra redradiation drying, air drying and the like.

Generally, the thickness of the hole transport layer is between about 5to about 100 micrometers, but thicknesses outside this range can also beused. The hole transport layer should be an insulator to the extent thatthe electrostatic charge placed on the hole transport layer is notconducted in the absence of illumination at a rate sufficient to preventformation and retention of an electrostatic latent image thereon. Ingeneral, the ratio of the thickness of the hole transport layer to thecharge generator layer is preferably maintained from about 2:1 to 200:1and in some instances as great as 400:1.

Other layers such as conventional ground strips comprising, for example,conductive particles dispersed in a film forming binder may be appliedto one edge of the photoreceptor in contact with the conductive surface,blocking layer, adhesive layer or charge generating layer.

Optionally, an overcoat layer may also be utilized to improve resistanceto abrasion. In some cases a back coating may be applied to the sideopposite the photoreceptor to provide flatness and/or abrasionresistance. These overcoating and backcoating layers may compriseorganic polymers or inorganic polymers that are electrically insulatingor slightly semi-conductive.

The electrophotographic member of the present invention containing theelectrically active polymeric arylamine in at least the generator ortransport layer may be employed in any suitable and conventionalelectrophotographic imaging process which utilizes charging prior toimagewise exposure to activating electromagnetic radiation. Conventionalpositive or reversal development techniques may be employed to form amarking material image on the imaging surface of the electrophotographicimaging member of this invention. Thus, by applying a suitableelectrical bias and selecting toner having the appropriate polarity ofelectrical charge, one may form a toner image in the negatively chargedareas or discharged areas on the imaging surface of theelectrophotographic member of the present invention. More specifically,for positive development, charged toner particles of one polarity areattracted to the oppositely charged electrostatic areas of the imagingsurface and for reversal development, charged toner particles areattracted to the discharged areas of the imaging surface. Where thetransport layer of this invention is sandwiched between aphotogenerating layer and a conductive surface, a positive polaritycharge is normally applied prior to imagewise exposure to activatingelectromagnetic radiation. Where the photogenerating layer layer of thisinvention is sandwiched between a transport layer and a conductivesurface, a negative polarity charge is normally applied prior toimagewise exposure to activating electromagnetic radiation.

The electrophotographic member of the present invention exhibits greaterresistance to cracking, crazing, crystallization of arylamine compounds,phase separation of arylamine compounds and leaching of arylaminecompounds during cycling.

The invention will now be described in detail with respect to thespecific preferred embodiments thereof, it being understood that theseexamples are intended to be illustrative only and that the invention isnot intended to be limited to the materials, conditions, processparameters and the like recited herein. All parts and percentages are byweight unless otherwise indicated.

EXAMPLE I Preparation of Polyhydroxy Ether Resin, Phenoxy Resin Based onN,N'-di(4-hydroxyphenyl)-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine, andbis(4-(2,3-epoxypropoxy)phenyl)-isopropylidene

To the reaction vessel are placed 5.2 grams (0.01 mole) of the dihydroxyarylamine compound and 3.4 grams (0.01 mole) of the diglycidyldiphenylene compound, 5 cc of p-dioxane and 0.52 gram (10⁻² mole/eq.weight of epoxide) of triphenyl phosphine (C₆ H₅)₃ P. The reactionmixture was heated to, and maintained at 102° C.±1 for 9 days. The veryviscous mass, which solidifies to a glass upon cooling to roomtemperature, was dissolved in a minimum of THF, and isolated by slowlyadding to 500 cc of MeOH in a Waring blender. Yield 85.6 percent. Mw15,368. Mn 7,433.

An aluminum plate bearing a vacuum deposited 0.5 micrometer layer ofamorphous selenium was coated with a tetrahydrofuran solution of theresulting polyhydroxyether resin (20 percent by weight solution) using a50 micrometer draw bar. A film having a dry thickness of ˜12 micrometerswas obtained after drying under vacuum for 12 hours. Flat plateelectrical scanning of this sample showed a V_(o) (charge acceptance) of900 V and a V_(R) (residual voltage) of ˜800 V. Exposure to Isopar L, anisoparaffinic hydrocarbon, for 1 week showed no small molecule leachingand no film cracking.

EXAMPLE II

The allylation of the phenoxy polymer is carried out in N-methylpyrolidinone (Aldrich Chemical Company), 10 milliliters (mls) in which 4grams of the polymer was dissolved. To this solution is added 1 gram ofpowdered KOH. To the now yellow solution was added CH₃ l, 2 mls, dilutedwith 5 mls of N-methyl pyrolidinone. This was allowed to stir for about2 hours. The reaction was quenched in 50 cc of MeOH. The white ppt wascollected by filtration. The infrared spectrum indicated all OH areblacked. Mw 15,200. Mn 5,400.

An aluminum plate bearing a vacuum deposited 0.5 micrometer layer ofamorphous selenium was coated with a tetrahydrofuran solution of theresulting alkylated polyethoxyether resin (20 percent by weight)solution using a 50 micrometer draw bar. A film having a dry thicknessof ˜12 micrometers was obtained after drying under vacuum for 12 hours.Flat plate electrical scanning of this sample showed a V_(o) (chargeacceptance) of 920 V and a V_(R) (residual voltage) of ˜0 V. Exposure toIsopar L, an isoparaffinic hydrocarbon, for 1 week showed no smallmolecule leaching and no film cracking.

EXAMPLE III Preparation of Polyhydroxyether Resin, Phenoxy Resin Basedon N,N'-diphenyl-N,N'-bis(3-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine,and bix (4-(2,3-epoxypropoxy)phenyl-isopropylidene

In a three-necked 250 round flask (flamed out) equipped with an Argonblanket, mechanical stirrer, thermostated oil bath is placed in thediepoxy phenylene compound DER 332, and the dihydroxy arylaminecompound. The oil bath is raised to 110° C. To the reaction mixture isadded 5 milliliters (mls) of dioxane and 0.1 gram triphenyl phosphine,(C₆ H₅)₃ P. The reaction mixture is a yellow color. The reaction iscontinued for 48 hours. During this period, dioxane is added, in 1milliliter portions, as needed to maintain stirring. The reaction isworked up by adding 50 mls of ThF to the cooling reaction flask. Thesolution was added to about 700 mls of MeOH in a Waring blender. Anoff-white solid was isolated. Mw 21,700, Mn 6,733.

An aluminum plate bearing a vacuum deposited 0.5 micrometer layer ofamorphous selenium was coated with a tetrahydrofuran solution of theresulting polyhydroxyether resin (20 percent by weight solution) using a50 micrometer draw bar. A film having a dry thickness of ˜12 micrometerswas obtained after drying under vacuum for 12 hours. Flat plateelectrical scanning of this sample showed a V_(o) (charge acceptance) of990 V and a V_(R) (residual voltage) of ˜0 V. Exposure to Isopar L, anisoparaffinic hydrocarbon, for 1 week showed no small molecule leachingand no film cracking.

EXAMPLE IV Preparation of Polyhydroxyether Resin Phenoxy Resin Based onN,N'-diphenyl-N,N'-bis (4-hydroxyphenyl)-[1,1'-biphenyl]-4,4'-diamine,andN,N'-diphenyl-N,N'-bis(4-(2,3-epoxypropoxy)phenyl)-[1,1'-biphenyl]-4,4'-diamine

The two reactants, 3.16 grams of the diepoxy arylamine compound, and 2.6grams of the dihydroxy arylamine compound are placed in a reactionvessel with 2 cc of dioxane and 0.026 gram of triphenyl phosphene. Thereaction was heated to and maintained at 105° C. for 3 days. Dioxane wasadded during this reaction period to maintain a viscosity suitable forstirring. The almost gel-like product was dissolved in N-Methylpyrolidinone and dioxane. The polymer was precipitation was accomplishedwith MeOH. Yield obtained was 78 percent. Mw 5,700. Mn 3,230.

An aluminum plate bearing a vacuum deposited 0.5 micrometer layer ofamorphous selenium was coated with a tetrahydrofuran solution of theresulting polyhydroxyether resin (50/50 percent by weight) using a 50micrometer draw bar. A film having a dry thickeness of ˜12 micrometerswas obtained after drying under vacuum for 12 hours. Flat plateelectrical scanning of this sample showed a V_(o) (charge acceptance) of980 V and a V_(R) (residual voltage) of ˜10 V. Exposure to Isopar L, anisoparaffinic hydrocarbon, for 1 week showed no small molecule leachingand no film cracking.

We claim:
 1. An electrostatographic imaging member comprising a supportlayer a charge generating layer and a charge transport layer, saidcharge transport layer comprising an arylamine compound represented bythe formula: ##STR24## wherein: R is selected from the group consistingof --H, --CH₃, and --C₂ H₅ ;m is between about 4 and about 1,000; and Ais selected from the group consisting of an arylamine group representedby the formula: ##STR25## wherein: m is 0 or 1, Z is selected from thegroup consisting of: ##STR26## wherein: n is 0 or 1, Ar is selected fromthe group consisting of: ##STR27## wherein: R is selected from the groupconsisting of --CH₃, --C₂ H₅, --C₃ H₇, and --C₄ H₉, Ar' is selected fromthe group consisting of: ##STR28## X is selected from the groupconsisting of: ##STR29## and B is selected from the group consistingof:the arylamine group as defined for A and

    --Ar--V).sub.n Ar--

wherein: Ar is as defined above, and V is selected from the groupconsisting of: ##STR30## and at least A or B contains the arylaminegroup, said arylamine compound being substantially non-photoconductivewhen exposed to radiation having a wavelength between about 4,000angstroms and about 9,000 angstroms, capable of supporting the injectionof photo-generated holes and capable of supporting the transport of saidholes.
 2. An electrostatographic imaging member according to claim 1wherein said charge transport layer is sandwiched between said supportlayer and said charge generating layer.
 3. An electrostatographicimaging member according to claim 1 wherein said charge generating layeris sandwiched between said support layer and said charge transportlayer.
 4. An electrostatographic imaging member comprising a supportlayer and at least one electrophotoconductive layer, said imaging membercomprising an arylamine compound represented by the formula: ##STR31##wherein: R is selected from the group consisting of --H, --CH₃, and --C₂H₅ ;m is between about 4 and about 1,000; and A is selected from thegroup consisting of an arylamine group represented by the formula:##STR32## wherein: m is 0 or 1, Z is selected from the group consistingof: ##STR33## wherein: n is 0 or 1, Ar is selected from the groupconsisting of: ##STR34## wherein: R is selected from the groupconsisting of --CH₃, --C₂ H₅, --C₃ H₇, and --C₄ H₉, Ar' is selected fromthe group consisting of: ##STR35## X is selected from the groupconsisting of: ##STR36## and B is selected from the group consistingof:the arylamine group as defined for A and

    --Ar--V).sub.n Ar--

wherein: Ar is as defined above, and V is selected from the groupconsisting of: ##STR37## and at least A or B contains the arylaminegroup, said arylamine compound being substantially non-photoconductivewhen exposed to radiation having a wavelength between about 4,000angstroms and about 9,000 angstroms, capable of supporting the injectionof photo-generated holes and capable of supporting the transport of saidholes.
 5. An electrostatographic imaging member according to claim 4wherein said imaging member comprises a charge generating layer and acharge transport layer and wherein said electrophotoconductive layer issaid charge generating layer.
 6. An electrostatographic imaging memberaccording to claim 5 wherein said charge generating layer comprisesphotogenerating pigment particles dispersed in a binder comprising saidarylamine compound.
 7. An electrostatographic imaging member accordingto claim 4 wherein said imaging member comprises a protectiveovercoating comprising said arylamine compound.
 8. Anelectrophotographic imaging process comprising forming an electrostaticlatent image on the imaging surface of an electrostatographic imagingmember comprising a support layer and at least oneelectrophotoconductive layer, said imaging member comprising anarylamine compound represented by the formula: ##STR38## wherein: R isselected from the group consisting of --H, --CH₃, and --C₂ H₅ ;m isbetween about 4 and about 1,000; and A is selected from the groupconsisting of an arylamine group represented by the formula: ##STR39##wherein: m is 0 or 1, Z is selected from the group consisting of:##STR40## wherein: n is 0 or 1, Ar is selected from the group consistingof: ##STR41## wherein: R is selected from the group consisting of --CH₃,--C₂ H₅, --C₃ H₇, and --C₄ H₉, Ar' is selected from the group consistingof: ##STR42## X is selected from the group consisting of: ##STR43## andB is selected from the group consisting of:the arylamine group asdefined for A and

    --Ar--V).sub.n Ar--

wherein Ar is as defined above, and V is selected from the groupconsisting of: ##STR44## at least A or B contains the arylamine group,said arylamine compound being substantially non-photoconductive whenexposed to radiation having a wavelength between about 4,000 angstromsand about 9,000 angstroms, capable of supporting the injection ofphoto-generated holes and capable of supporting the transport of saidholes, and contacting said imaging member with a developer to deposittoner marking particles on said imaging surface to form a markingparticle image in conformance to said electrostatic latent image.
 9. Anelectrophotographic imaging process according to claim 8 wherein saiddeveloper is a liquid developer.
 10. An electrophotographic imagingprocess according to claim 9 wherein said liquid developer comprises anorganic carrier fluid.
 11. An electrophotographic imaging processaccording to claim 9 including transfering said marking particle imageto a receiving member.
 12. An electrophotographic imaging processaccording to claim 11 including repeating said forming, contacting andtransfering steps at least once.
 13. An electrophotographic imagingprocess according to claim 8 wherein said imaging member comprises acharge generating layer and a charge transport layer comprising saidarylamine compound, said charge transport layer being substantiallytransparent to radiation in the region in which said imaging member isexposed during electrophotographic imaging and capable of supporting theinjection of photo-generated holes from said charge generating layer andtransporting said holes through said charge transport layer toselectively discharge an electrostatic charge on said image surface toform said electrostatic latent image.